Locomotion behavior testing as a complementary tool in Collembola avoidance assays with neurotoxic insecticides.

This study aimed (1) to assess the ability of collembolans Folsomia candida to avoid soils contaminated with three seed dressing insecticides imidacloprid, clothianidin, and fipronil; (2) to assess the effects of the insecticides on collembolans' locomotion behavior; (3) to check if changes in the locomotion behavior would explain the avoidance/preference responses; and (4) to evaluate the possibility to use locomotion behavior as toxicity biomarker of the tested insecticides. Avoidance and locomotion behavior assays with collembolans F. candida were performed with commercial seed dressing formulations of three insecticides (imidacloprid, clothianidin, and fipronil). Results showed no avoidance behavior at any concentration, while a "preference" was observed with increasing concentrations of the three tested insecticides. Significant reductions in the locomotion of exposed collembolans were observed at ≥ 1 mg kg-1 for imidacloprid (18-38%) and fipronil (29-58%) and ≥ 4 mg kg-1 for clothianidin (10-47%). At the higher insecticide concentrations, the collembolans had their trajectories restricted to smaller areas, with a tendency for circular movements. Our results confirm that the "preference" for contaminated soils with neurotoxic substances is likely due to locomotion inhibition impairing the ability of organisms to escape. This effect highlights that only avoidance assays may be not sufficient to assure the safety of some substances and confirm the potential of locomotion behavior as a sensitive toxicity biomarker for neurotoxic insecticides.

A systematic review of the toxic effects of a nanopesticide on non-target organisms: Estimation of protective concentrations using a species sensitivity distribution (SSD) approach - The case of atrazine.

Nanopesticides, such as nanoencapsulated atrazine (nATZ), have been studied and developed as eco-friendly alternatives to control weeds in fields, requiring lower doses. This review contains a historical and systematic literature review about the toxicity of nATZ to non-target species. In addition, the study establishes protective concentrations for non-target organisms through a species sensitivity distribution (SSD) approach. Through the systematic search, we identified 3197 publications. Of these, 14 studies addressed "(nano)atrazine's toxicity to non-target organisms". Chronological and geographic data on the publication of articles, characterization of nATZ (type of nanocarrier, size, polydispersity index, zeta potential), experimental design (test species, exposure time, measurements, methodology, tested concentrations), and toxic effects are summarized and discussed. The data indicate that cell and algal models do not show sensitivity to nATZ, while many terrestrial and aquatic invertebrates, aquatic vertebrates, microorganisms, and plants have high sensitivity to nAZT. The SSD results indicated that D. similis is the most sensitive species to nATZ, followed by C. elegans, E. crypticus, and P. subcapitata. However, the limitations in terms of the number of species and endpoints available to elaborate the SSD reflect gaps in knowledge of the effects of nATZ on different ecosystems.

Rapid Communication: oxidative stress induced by mixed exposure to glyphosate and silver nanoparticles.

The aim of this study was to examine oxidative stress induced by the binary mixture of silver nanoparticles (AgNP) and glyphosate (Gly) in Daphnia magna by measurement of reactive oxygen species (ROS) production, glutathione (GSH) levels, enzyme activities of catalase (CAT) and superoxide dismutase (SOD) as well as malondialdehyde (MDA) content. Acute exposure of Daphnia magna to binary mixture of AgNP and Gly resulted in significant biochemical responses indicative of oxidative damage. This response seemed to be related to imbalance in enzymatic/non-enzymatic antioxidant enzymes associated with intracellular overproduction of ROS and significant increase in MDA levels, indicating that the integrity and function of the cell membrane was damaged. These changes adversely affected the fitness and survival of Daphnia magna and negatively influenced offspring growth and reproduction.

Application of a phosphonium-based ionic liquid for reactive textile dye removal: Extraction study and toxicological evaluation.

Textile dyeing processes are known for their negative environmental impacts due to the production of aqueous effluents containing toxic dyes. Therefore, new wastewater treatment processes need to be developed to treat such effluents, including Liquid-Liquid Extraction (LLE) process using Ionic Liquids (IL). This work aimed to evaluate the application of the hydrophobic IL trihexyltetradecylphosphonium decanoate to extract black, navy, and royal reactive dyes from water and evaluate the toxicological aspects of the resulting water stream. We investigated the effect of selected parameters, such as pH (2-12), temperature (20-50 °C), salt effects, dye concentration (0.5-50 mg/L), and phase volume ratio (900-9000) on the dye extraction. The results showed extraction yields as high as 97% for the three dyes and an extraction capacity of approximately 300 mg/g for black and navy dyes and 400 mg/g for royal. The toxicity tests involved Lactuca sativa, Triticum aestivium L, and Daphnia magna as bioindicators. The difference between the toxicity of the dye solutions before and after extraction was not statistically significant when L. sativa and Triticum aestivum L were used as bioindicators. However, the extracted solution showed increased toxicity towards D. magna due to traces of IL. Overall, the IL has a high extraction capacity for the black, navy, and royal dyes. Nevertheless, further studies on LLE associated with other processes must be carried out to reduce the risk linked to the toxicity of IL transferred to the water.

Membrane adsorption with polyacrylonitrile prepared with superfine powder-activated carbon, case study: separation process applied in water treatment containing diclofenac.

Polyacrylonitrile membranes (PAN) have high stability against chemical agents, making them suitable for a wide range of applications as such Ultrafiltration processes. Ultrafiltration membranes composed of PAN/Superfine powder activated carbon (S-PAC) mixtures can be a good research route, aiming the development of a new separation processes for water treatment. The association of materials to form a single product can have technological and economic advantages in separation processes. In this study, S-PAC impregnated into PAN membranes were prepared, characterized and used, as a case study, to remove diclofenac (DCF) from water. The membranes (PAN/S-PAC) were synthesized with different concentrations of S-PAC (0.2, 0.6, 1.0, 3.0 and 5.0 wt%) by a phase inversion process. The results of the TEM characterizations of the S-PAC indicated the presence of micro and nanoparticles (∼10 nm) and tending to form micrometric clusters. The infrared spectra of the membranes were characteristic of PAN; however, vibrational bands attributed to the S-PAC spectrum were also observed, which indicated an interaction between the materials. The case study showed an increase in the water flux and in the DCF rejection efficiency, for composite membranes (PAN/S-PAC) with higher concentration of S-PAC. The results of static adsorption tests indicated that the mechanism of DCF rejection occurred predominantly by adsorption. There were indications that the PAN/S-PAC membranes formed a composite material and the PAN/S-PAC (3.0) presented the best study composition given the results. Although the research is in its initial phase, the results indicated that the composition can improve many water treatment systems.

Toxicological effects of leachate extracts from asphalt mixtures nanomodified under Daphnia magna and Landoltia punctata test organisms.

The incorporation of nanomaterials in binders in the paving area has been studied to improve the mechanical behavior of asphalt mixtures. However, asphalt mixture compounds are susceptible to leaching and deposition in the environment. In this context, this research aimed to investigate the toxic effect of two leachate extracts from asphalt mixtures nanomodified with 2% carbon nanotube and 3% organophilic nanoclay, compared to conventional mixture, using Daphnia magna and Landoltia punctata as test organisms. The nanomaterials were characterized to confirm morphology, stability and effective diameter. Extracts were chemically characterized using the Fourier-Transform Infrared Spectroscopy (FTIR) technique, which indicated presence of functional groups of the asphalt binder in greater intensity in the leachate from conventional mixture. Acute toxicity with D. magna indicated EC50,48h of 83.5 ± 6.2 mL/L for leachate extract from conventional mixture, 306.0 ± 87.6 mL/L for leachate extract from mixture with nanoclay and 464.8 ± 32.1 mL/L for leachate extract from mixture with carbon nanotube. No leachate caused significant chronic toxicity. As for L.punctata, concentrations that caused 50% growth inhibition were 127.5 mL/L for the leachate extract from mixture with carbon nanotube, 196.9 mL/L for the leachate extract from mixture with nanoclay and 205 mL/L for the leachate extract from conventional mixture. For these test organisms, there is no evidence of negative impacts directly associated with the use of the present nanomaterials in asphalt mixtures. The incorporation of these nanos may also reduce the acute toxicity of the mixtures.

Acute and chronic toxicity of amine-functionalized SiO2 nanostructures toward Daphnia magna.

Silicon oxide (SiO2) nanostructures (SiO2NS) are increasingly being incorporated into an array of products, notably in the food, pharmaceutical, medical industries and in water treatment systems. Amorphous SiO2NS have low toxicity, however, due to their great versatility, superficial modifications can be made and these altered structures require toxicological investigation. In this study, SiO2NS were synthetized and amine-functionalized with the molecules (3-aminopropyl)triethoxysilane (APTMS) and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEAEAPTMS), named SiO2NS@1 and SiO2NS@3, respectively. The bare SiO2NS, SiO2NS@1 and SiO2NS@3 samples were characterized and the influence of the culture medium used in the toxicological assays was also evaluated. The effect of amine functionalization of SiO2NS was investigated through acute and chronic toxicity assays with Daphnia magna. Modifications to ultrastructures of the intestine and eggs of these organisms were observed in TEM and SEM analysis. The toxicity was influenced by the surface modifications and a possible Trojan horse effect was highlighted, particularly in the case of chronic exposure. Exposure to all NSs promoted alterations in the microvilli and mitochondria of the D. magna intestine and some damage to egg cells was also observed. The results demonstrate the importance of carrying out a full characterization of these materials, since surface modifications can enhance their toxic potential.

Toxicity of leachates from pilot reactors simulating a landfill with different concentrations of AgNP / Toxicidade dos lixiviados de reatores-piloto simulando um aterro com diferentes concentrações de NPAg

ABSTRACT This work's objective was to verify the leachates toxicity from pilot reactors (PR) simulating a landfill containing different concentrations of silver nanoparticles (AgNP). Acute toxicity tests (48 h) with Daphnia magna were carried out in leachates containing 50, 150 and 450 mg AgNP.kg-1, in addition to a blank for control. Toxicity tests with the pure solution of silver nanoparticle and leachates resulted by the reactors were performed. The acute toxicity tests performed with D. magna confirmed the toxicity of the leachates, as well as confirmed that the silver nanoparticles are toxic, presenting EC50 (48 h) of 0.63 µg.L-1 of pure nanoparticle and ranging from 1.52 to 3.37% for the leachates. Overall, the results from the present study indicate that exposures of aquatic invertebrates to silver nanoparticles could have important ecological effects on lower trophic levels in aquatic ecosystems. The results may contribute to a better understanding of the quality of municipal solid waste (MSW) landfill leachates, with reference to nanoparticle interference and consequent treatment efficiency.

RESUMO O objetivo deste trabalho foi verificar a toxicidade de lixiviados de reatores piloto (RP) simulando um aterro contendo diferentes concentrações de nanopartículas de prata (AgNP). Testes de toxicidade aguda (48 h) com Daphnia magna foram realizados em lixiviados contendo 50, 150 e 450 mg de AgNP.kg-1, além de um branco para controle. Foram realizados testes de toxicidade com a solução pura de nanopartículas de prata e lixiviados resultantes dos reatores. Os testes de toxicidade aguda realizados com D. magna confirmaram a toxicidade dos lixiviados, bem como confirmaram que as nanopartículas de prata são tóxicas, apresentando EC50 (48 h) de 0,63 µg.L-1 de nanopartículas puras e variando de 1,52 a 3,37% para os lixiviados. No geral, os resultados do presente estudo indicam que a exposição dos invertebrados aquáticos a nanopartículas de prata pode ter importantes efeitos ecológicos nos níveis tróficos inferiores nos ecossistemas aquáticos. Os resultados podem contribuir para a melhor compreensão da qualidade dos lixiviados de aterros sanitários de resíduos sólidos urbanos (RSU), com referência à interferência de nanopartículas e consequente eficiência de tratamento destes.

Toxicological Evaluation and Quantification of Ingested Metal-Core Nanoplastic by Daphnia magna Through Fluorescence and Inductively Coupled Plasma-Mass Spectrometric Methods.

There are few studies on nanoplastic that propose quantification of the amount ingested combined with evaluation of the toxic effects on aquatic organisms. We propose 2 methods to quantify the amount of polystyrene nanoplastic (PSNP) ingested by Daphnia magna: fluorescence intensity, where a fluorescent monomer (F) is added to the PSNP and quantified through fluorescence light microscopy, and total aluminum quantification, where PSNP is synthesized with Al2 O3 metal-core nanoparticles and used for quantification of the nanoplastic ingested by the organism Daphnia magna using inductively coupled plasma-mass spectrometry. In addition, the PSNP was functionalized with palmitic acid to simulate the environmental conditions leading to biological and chemical transformations. Acute and chronic toxicity tests were performed with fluorescent PSNP (PSNP/F) and palmitic acid-functionalized PSNP/F (PSNP/F-PA). The ingestion quantified was higher by factors of 2.8 and 3.0 for PSNP/F-PA and 1.9 and 1.7 for PSNP/F applying the fluorescence intensity and total Al quantifying methods, respectively, when compared to PSNP. These results are consistent with the data obtained in the toxicity tests, which showed an approximately 3 times increase in the adverse effect of PSNP/F-PA on the mobility and reproduction of the organisms. Thus, the strong inhibition of D. magna reproduction caused by PSNP/F-PA in the chronic toxicity tests could be associated with a greater amount of this nanoplastic being ingested by the organisms. Environ Toxicol Chem 2019;38:2101-2110. © 2019 SETAC.

Investigation of toxicological effects of amorphous silica nanostructures with amine-functionalized surfaces on Vero cells.

Amorphous silica (SiO2) nanostructures are described in the literature as having low toxicity and are widely used in many industrial products. However, surface modifications, such as amine-functionalization, can result in increased cytotoxicity. In this study, amorphous SiO2 nanostructures (SiO2 NS) were synthesized and amine-functionalized with two different amine molecules: primary (SiO2 NS@1) and tri-amine (SiO2 NS@3). The materials were characterized by transmission electron microscopy (TEM), zeta potential (ZP), effective diameter (ED) and surface area measurements, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The toxicity of the three SiO2 NS samples toward Vero cells was evaluated. According to the methyl thiazolyl tetrazolium (MTT) assay, the IC50,24h was 1.477 ±â€¯0.12 g L-1 for SiO2 NS, 0.254 ±â€¯0.07 g L-1 for SiO2 NS@1 and 0.117 ±â€¯0.05 g L-1 for SiO2 NS@3. The order of cytotoxicity was SiO2 NS@3 > SiO2 NS@1 ¼ SiO2 NS. There was an increase in malondialdehyde (MDA) levels and ROS productions in the cells exposed to all three materials. Also, TEM images showed damage on the mitochondria and rough endoplasmic reticulum.

Synthesis, characterization and toxicological evaluation of Cr2O3 nanoparticles using Daphnia magna and Aliivibrio fischeri.

Chromium III oxide (Cr2O3) nanoparticles (NPs) are used in pigments for ceramics, dyes, paints and cosmetics. However, few studies addressing the toxic potential of these NPs have been reported in the literature. Thus, this research aimed to evaluate the acute and chronic effects of Cr2O3 NPs through acute toxicity tests with Daphnia magna and Aliivibrio fischeri and chronic toxicity tests with Daphnia magna. Cr2O3 NPs were synthesized by the sol-gel method and characterized through TEM, X-Ray diffraction (XRD), zeta potential (ZP) and surface area analysis. In the acute toxicity tests the EC(50,48h) value obtained with D. magna was 6.79 mg L(-1) and for A. fischeri the EC(50,15min) value was 16.10 mg L(-1) and the EC(50,30min) value was 12.91 mg L(-1). Regarding the chronic toxicity tests with D. magna, effects on longevity (OEC=1.00 mg L(-1)), reproduction (OEC=1.00 mg L(-1)) and growth (OEC=0.50 mg L(-1)) were observed. On the SEM and TEM images, ultrastructural alterations in the organelles of exposed organisms were also observed. Thus, toxicological studies with NPs are of great importance in order to reduce the risk of environmental contamination.